Professional Documents
Culture Documents
Urea Manufacturing Plant: CH 4200 - Comprehensive Design Project
Urea Manufacturing Plant: CH 4200 - Comprehensive Design Project
Project Coordinator: Dr. Maneesha Gunasekara Group Members: G.A.M.C. Ariyathilaka A.N. Buddhika K.R.M.G. Kahatapitiya K.D.N. Karunarathna D.D.D.P.Sandasiri
Comprehensive design project
ACKNOWLEDGEMENT
First of all we would like to grant our heartiest gratitude to our project coordinator, Dr. Maneesha Gunasekara (lecturer- Chemical & Process Engineering department, University of Moratuwa) for all the guidance and support that she has given us to complete this design project in a successful manner. Dear Madam, please expect our sincere thanks for your kind hearted support and genuine friendly attitude shown towards our work. Thank you very much for spending your precious time to share your knowledge & experience with us. Then again, we must not forget all the staff members of Chemical & Process Engineering department, including the head of the department Dr. Jagath Premachandra , for all the assistance and support given us for accomplish the project. Without your support we may have not come this far, so please accept our sincere thanks .Also we thank the level-4, semester-1 coordinator, Dr. Suren Wijekoon, lecturer- Chemical & Process Engineering Department, University of Moratuwa. And finally, a special thank should be given to the staff of Sri Lanka Custom Office who provide us data related to urea imports.
Thank you, G.A.M.C. Ariyathilaka A.N. Buddhika. K.R.M.G. Kahatapitiya K.D.N. Karunarathna D.D.D.P.Sandasiri
PREFACE
The final year project is task, where we apply our knowledge & experience, gained throughout the four year degree course, in a practical scenario. Here we have done it in our best capacity. It is a step which finally determines the capability to perform as chemical engineers. The ultimate goal of the final year design project on urea manufacturing plant is to find out the feasibility of setting up such a plant in Sri Lanka. In Sri Lanka urea is being used as a fertilizer in the agriculture sector. Other than as a fertilizer, urea is hardly used in any industry or any other sector even though urea has number of industrial and commercial uses. Sri Lanka imports urea from other countries such as Saudi Arabia, India, and China. The total import volume of urea is around 330,000 MT per annum. Sri Lankan government gives urea fertilizer in subsidized price for farmers. From the budget 2008, Sri Lanka allocated 15 billion rupees for fertilizer subsidies. However in the past with the establishment of The Urea Plant at Sapugaskanda, Sri Lanka became self sufficient in fertilizer requirements of the country. In 1982, the annual production of urea at Sapugaskanda factory was 310,000 tons. Then the country's annual demand was only 290,000 tons. The excessive production of 20,000 tons of urea was exported earning foreign exchange around Rs. 200 million. In 1982 the annual savings of State Fertilizer Corporation stood at Rs.750 million. In addition it had provided direct employment opportunities to 1,250 workers. Sapugaskanda Urea plant was closed in January 1987. In the world point of view urea is produced on a scale of some 100,000,000 tons per year worldwide. Urea is produced from synthetic ammonia and carbon dioxide. Urea can be produced as prills, granules, flakes, pellets, crystals, and solutions. More than 90% of world production is destined for use as a fertilizer. Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use (46.7%).Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer solutions. Solid urea is marketed as prills or granules. The advantage of prills is that, in general, they can be produced more cheaply than granules, which, because of their narrower particle size distribution, have an advantage over prills if applied mechanically to the soil. In Sri Lanka establishing urea manufacturing plant has many advantages. It will have greater effect on countrys economy, development in agriculture sector, providing employment and other tangible and intangible benefits. But without having an ammonia Comprehensive design project II
Urea Manufacturing Plant production process from which in most cases raw materials for urea manufacturing (ammonia and carbon dioxide) is derived, it is rather difficult and unfeasible to establish a urea plant along considering the availability of raw materials. Considering the project it is presumed that ammonia and some instance carbon dioxide is imported. According to the current demand of Sri Lanka, the urea demand of the country with in next five years will be around 350,000 MT per annum. So we decided to design a Urea manufacturing plant to fulfill that requirement. Our plant is operated for 328 days per year. And rest of the year can be allocated for maintenance of the plant. Constructing of this kind of manufacturing plant will enhance the countrys development since the ultimate product urea is directly related with countrys economy and growth in agriculture sector and a utility for many other industries. On the other hand the global demand for urea is increasing rapidly; specially in Asian countries. Under those circumstances we present the final year comprehensive design project which would be beneficial for countrys development. The design project is combined in to this report, consist of 8 chapters. Chapters include Literature survey, Process selection and Economic aspects, Process description and Flow sheet, Site selection, Mass balance calculation, Material flow sheet, Heat balance calculation, Tabulated heat balance.
CONTENTS
Chapter 01
Page No
1.0 Literature Survey... 1.1 Urea .. 1.1.1 Synthetic urea . 1.1.2 Commercial production of urea .. 1.1.3 Chemical characteristics of urea 1.1.4 Physical characteristics of urea .. 1.1.5 Raw materials of urea manufacturing 1.1.5.1 Ammonia . 1.1.5.1.1 Ammonia Production 1.1.5.1.2 Ammonia storage . 1.1.5.2 Carbon Dioxide ....... 1.1.6 Applications of urea... 1.1.6.1 Agricultural use 1.1.6.1.1 Advantages of Fertilizer Urea.. 1.1.6.1.2 Soil Application and Placement of Urea.. 1.1.6.1.3 Spreading of Urea 1.1.6.2 Industrial use 1.1.6.3 Further commercial uses.. 1.1.6.4 Laboratory use. 1.1.6.5 Medical use. 1.1.6.5.1 Drug use .. 1.1.6.5.2 Diagnostic use 1.1.6.6 Textile use 1.2 Global production and consumption of Urea.. 1.2.1 Range of global uses of urea.. 1.3 Urea Prices.. 1.4 Urea Production and Consumption in Sri Lanka
02 02 02 02 03 04 04 04 05 06 06 06 06 07 07 08 08 08 10 10 10 10 10 11 14 15 15
Chapter 2
2.0 Process Selection & Economic Aspects.. 2.1 Feasibility Study.. Comprehensive design project IV 18 18
Urea Manufacturing Plant 2.1.1 Introduction 2.1.2 Technical & Economic Feasibility 2.1.2.1 Plant Capacity. 2.1.3 Social & Environmental Feasibility 2.1.4 Plant Components.. 2.2 Process Selection. 2.2.1 Conventional Processes. 2.2.1.1 Once through Process.. 2.2.1.2 Conventional Recycle Process 2.2.2 Stamicarbon CO2 stripping process 2.2.3 Snamprogetti Ammonia and self stripping processes 2.2.4 Isobaric double recycle process 2.2.5 ACES process 2.2.6 Process comparison 2.2.6.1 Advantages of ACES Process. 18 19 19 20 20 21 21 21 21 24 27 28 29 29 30
Chapter 3
3.0 Process Description and flow sheet 3.1 Process Description ACES Process. 3.1.1 ACES Urea plants available in the world.. 3.2 Main component of the process. 3.2.1 Reactor.. 3.2.2 Stripper.. 3.2.3 Carbamate Condenser 3.2.4 Scrubber 3.2.5 Medium Pressure Decomposer.. 3.2.6 Low Pressure Decomposer 3.2.7 Medium Pressure Absorber... 3.2.8 Low Pressure Absorber. 3.2.9 Flash Separator.. 3.2.10 Lower Separator.. 3.2.11 Upper Separator.. 3.2.12 Granulation Plant. 3.3 Typical product quality... Comprehensive design project V 32 32 34 34 34 34 35 35 35 35 35 36 36 36 36 37 38
Chapter 4
4.0 Site Selection & Plant Layout. 4.1 Site Selection 4.1.1 Availability of raw materials.. 4.1.2 Infrastructure facilities 4.1.3 Legal obligations enforced by relevant authority or the government 4.1.4 Environment and Climate Conditions 4.1.5 Labour Force availability 4.1.6 Social considerations. 4.1.7 Waste Management... 4.2 Plant Layout 4.2.1 Importance .... 4.3 Environmental Impact Assessment. 4.3.1 Objectives of EIA Assessment.. 4.3.2 Impact of the Urea Plant on the environment 4.3.3 Emissions to Air 4.3.4 Emissions to Water 4.3.5 Emissions to Land.. 4.3.6 Elimination Methods. 4.4 Safety Of the Urea Plant.. 4.4.1 Safety factors relevant to urea .. 4.4.2 Safety Factors Relevant to Ammonia 4.4.3 Safety Factors Relevant to Ammonium Carbamate 4.4.4 Safety Factors Relevant to Biurete (byproduct) 40 40 40 41 42 42 42 42 43 43 43 44 44 45 46 46 46 47 49 50 53 57 60
Chapter 5
5.0 Mass Balance Calculation.. 5.1 Material Balance 5.1.1 Reactor.. 5.1.2 Stripper.. 5.1.3 Carbamate Condenser 5.1.4 Scrubber 5.1.5 High Pressure Decomposer... 5.1.6 Low Pressure Decomposer Comprehensive design project VI 64 64 66 67 68 69 70 71
Urea Manufacturing Plant 5.1.7 Low Pressure Absorber. 5.1.8 Medium Pressure Absorber 5.1.9 Flash Separator.. 5.1.10 Lower Separator.. 5.1.11 Upper Separator... 5.1.12 Waste Water Treatment Unit... 5.1.13 Granulator 5.1.14 Screen... 5.1.15 Product Cooler. 5.1.16 Bag Filter. 72 73 74 75 76 77 78 79 80 81
Chapter 6
Material Flow Sheet 83
Chapter 7
7.0 Heat Balance Calculation 7.1 Main Process Energy Balance 7.1.1 Reactor.. 7.1.2 Stripper.. 7.1.3 Scrubber. 7.1.4 Carbamate Condenser 7.1.5 High pressure decomposer 7.1.6 Low pressure decomposer 7.1.7 Low pressure absorber.. 7.1.8 High pressure absorber.. 7.1.9 Flash separator.. 7.1.10 Lower separator.. 7.1.11 Upper separator... 7.1.12 Process wastewater treatment unit.. 7.2 Granulation Plant 7.2.1 Granulator. 7.2.2 Product cooler... 85 85 88 90 91 93 95 96 98 99 101 102 103 104 105 105 105
Chapter 8
8.0 Tabulated Heat Balance.. Comprehensive design project VII 107
References ...
109
List of Figures
Figure 1.1 Chemical structures of urea molecules Figure 1.2 (a) The change in world consumption. Figure 1.3: Global distribution of the consumption of urea fertilizer.. Figure 1.4 Urea import data.. Figure 2.1 Conventional process flow diagram Figure 2.2 CO2 stripping process flow diagram Figure 3.2 Functional block diagram of the ACES Figure 3.1 Process Flow Sheet.. Figure 3.3 Pipe and Instrumentation diagram Figure 3.4 Granulation plant Figure 3.5 Spout-Fluid Bed Granulator. Figure 3.6 Power Consumption of Spout-Fluid Bed Granulation. Figure 3.7 Various sizes of granules Figure 4.1 Plant layout.. Figure 6.1 Material Flow Sheet.
Page No
03 11 13 16 23 26 32 32 33 37 37 38 38 43 83
List of Tables
Table1.1 chemical characteristics of urea. Table 1.2 Physical Characteristics of Urea Table 1.3 Urea Prices Table 3.1 ACES Urea plants available in the world Process. Table 4.1 Ammonia releases from urea plants.. Table 4.2 Typical consumption figures for a granulation plant Table 4.3 Emissions from Urea manufacturing process.. Table 5.1 Compound in urea manufacturing. Table 8.1 Tabulated Heat Balance
Page No
04 04 15 34 45 45 45 65 107
Chapter 01
CHAPTER 1
LITERATURE SURVEY
Chapter 01
Chapter 01
reactants. The various urea processes are characterized by the conditions under which urea formation takes place and the way in which unconverted reactants are further processed. Unconverted reactants can be used for the manufacture of other products, for example ammonium nitrate or sulfate, or they can be recycled for complete conversion to urea in a totalrecycle process. Two principal reactions take place in the formation of urea from ammonia and carbon dioxide. The first reaction is exothermic: 2 NH3 + CO2 H2N-COONH4 (ammonium carbamate) Whereas the second reaction is endothermic: H2N-COONH4 (NH2)2CO + H2O Both reactions combined are exothermic.
The urea molecule is planar and retains its full molecular point symmetry, due to conjugation of one of each nitrogen's P orbital to the carbonyl double bond. Each carbonyl oxygen atom accepts four N-H-O hydrogen bonds, a very unusual feature for such a bond type. This dense (and energetically favorable) hydrogen bond network is probably established at the cost of efficient molecular packing: The structure is quite open, the ribbons forming tunnels with square cross-section. Urea is stable under normal conditions.
Urea Manufacturing Plant IUPAC name Chemical formula Molecular mass Dipole moment pH Diaminomethanal (NH2)2CO 60.07 g/mol (approximate) 4.56 p/D (100g.L-1 in water, 20C) ~9
Chapter 01
1.1.4 Physical characteristics of urea Urea is a white odourless solid. Due to extensive hydrogen bonding with water (up
to six hydrogen bonds may form - two from the oxygen atom and one from each hydrogen) urea is very soluble.
1.3310 kg/m, solid 132.7 C (406 K) decomposes NA 108 g/100 ml (20 C) 167 g/100 ml (40 C)
Solubility in water
Chapter 01
ammonia vapour can be fatal. When dissolved in water, elevated levels of ammonia are also toxic to a wide range of aquatic organisms. Ammonia is highly soluble in water, although solubility decreases rapidly with increased temperature. Ammonia reacts with water in a reversible reaction to produce ammonium (NH 4)+ and hydroxide (OH) - ions, as shown in equation. Ammonia is a weak base, and at room temperature only about 1 in 200 molecules are present in the ammonium form (NH4)+. The formation of hydroxide ions in this reaction increases the pH of the water, forming an alkaline solution. If the hydroxide or ammonium ions react further with other compounds in the water, more ammonia with react to reestablish the equilibrium. NH3 + H2O
(NH4) + OH
+ -
While ammonia-air mixtures are flammable when the ammonia content is 16-25% by volume, these mixtures are quite difficult to ignite. About 85% of the ammonia produced worldwide is used for nitrogen fertilizers. The remainder is used in various industrial products including fibers, animal feed, and explosives.
1.1.5.1.1 Ammonia Production Essentially all the processes employed for ammonia synthesis are variations of the Haber-Bosch process, developed in Germany from 1904-1913. This process involves the reaction of hydrogen and nitrogen under high temperatures and pressures with an iron based catalyst. This process also requires large energy consumption. Ammonia is generally produced at a few large plants with stream capacities of 1000 tonnes/day or greater. The formation of ammonia from hydrogen and nitrogen is a reversible reaction, as shown in equation [2]. The fraction of ammonia in the final gas mixture is dependent on the conditions employed. Unreacted hydrogen and nitrogen gases separated from the ammonia and are usually recycled. In almost all modern plants, the ammonia produced is recovered by condensation to give liquid ammonia. H2 + 3N2 2NH3
The source of nitrogen is always air. Hydrogen can be derived from a number of raw materials including water, hydrocarbons from crude oil refining, coal, and most commonly natural gas. Hydrogen rich reformer off-gases from oil refineries have also been used as a source of hydrogen. Steam reforming is generally employed for the production of hydrogen from these raw materials. This process also generates carbon dioxide, which can then be used as a raw material in the production of urea. Comprehensive design project 5
Chapter 01
Trace impurities in the feed gases, such as sulphur compounds and chlorides, can have a detrimental effect on the production of ammonia by poisoning the catalysts employed. The feed gases, therefore, need to be purified prior to use.
1.1.5.1.2 Ammonia storage Anhydrous ammonia is usually stored as a liquid in refrigerated tanks at 33.3 C and atmospheric pressure, often in doubled-walled tanks with the capacity for hundreds or thousands of tonnes. The low temperature is usually maintained by the venting of ammonia gas. The vented gas is reliquefied for recycling, or absorbed in water to make aqueous ammonia. Relatively small quantities of anhydrous ammonia are sometimes stored under pressure in spherical vessel at ambient temperature. Ammonia is corrosive to alloys of copper and zinc and these materials must never be used in ammonia service. Iron and steel are usually the only metals used in ammonia storage tanks, piping and fittings.
1.1.5.2 Carbon Dioxide CO2 is a odourless and colourless gas which contain 0.03% in the atmosphere. It is emitted as a pollutant from number of industries. CO2 can be obtained from ammonia production process as a by product.
Chapter 01
the product. The prills formed a smaller and softer substance than other materials commonly used in fertilizer blends. Today, though, considerable urea is manufactured as granules. Granules are larger, harder, and more resistant to moisture. As a result, granulated urea has become a more suitable material for fertilizer blends. 1.1.6.1.1 Advantages of Fertilizer Urea Urea can be applied to soil as a solid or solution or to certain crops as a foliar spray. Urea usage involves little or no fire or explosion hazard. Urea's high analysis, 46% N, helps reduce handling, storage and transportation costs over other dry N forms. Urea manufacture releases few pollutants to the environment. Urea, when properly applied, results in crop yield increases equal to other forms of nitrogen. Nitrogen from urea can be lost to the atmosphere if fertilizer urea remains on the soil surface for extended periods of time during warm weather. The key to the most efficient use of urea is to incorporate it into the soil during a tillage operation. It may also be blended into the soil with irrigation water. A rainfall of as little as 0.25 inches is sufficient to blend urea into the soil to a depth at which ammonia losses will not occur. Urea breakdown begins as soon as it is applied to the soil. If the soil is totally dry, no reaction happens. But with the enzyme urease, plus any small amount of soil moisture, urea normally hydrolizes and converts to ammonium and carbon dioxide. This can occur in 2 to 4 days and happens quicker on high pH soils. Unless it rains, urea must be incorporated during this time to avoid ammonia loss. Losses might be quite low if the soil temperature is cold. The chemical reaction is as follows: CO(NH2)2 + H2O + urease 1.1.6.1.2 Soil Application and Placement of Urea The volatility of urea depends to a great extent on soil temperature and soil pH. If properly applied, urea and fertilizers containing urea are excellent sources of nitrogen for crop production. After application to the soil, urea undergoes chemical changes and ammonium (NH 4 +) ions form. Soil moisture determines how rapidly this conversion takes place. When a urea particle dissolves, the area around it becomes a zone of high pH and ammonia concentration. This zone can be quite toxic for a few hours. Seed and seedling roots Comprehensive design project 7 2NH3 +CO2
Chapter 01
within this zone can be killed by the free ammonia that has formed. Fortunately, this toxic zone becomes neutralized in most soils as the ammonia converts to ammonium. Usually it's just a few days before plants can effectively use the nitrogen. Although urea imparts an alkaline reaction when first applied to the soil, the net effect is to produce an acid reaction. Urea or materials containing urea should, in general, be broadcast and immediately incorporated into the soil. Urea-based fertilizer applied in a band should be separated from the seed by at least two inches of soil. 1.1.6.1.3 Spreading of Urea Urea can be bulk-spread, either alone or blended with most other fertilizers. Urea often has a lower density than other fertilizers with which it is blended. This lack of "weight" produces a shorter "distance-of-throw" when the fertilizer is applied with spinner-type equipment. In extreme cases this will result in uneven crop growth and "wavy" or "streaky" fields. Urea and fertilizers containing urea can be blended quite readily with monoammonium phosphate (11-52-0) or diammonium phosphate (18-46-0). Urea should not be blended with superphosphates unless applied shortly after mixing. Urea will react with superphosphates, releasing water molecules and resulting in a damp material which is difficult to store and apply. Urea fertilizer can be coated with certain materials, such as sulfur, to reduce the rate at which the nitrogen becomes available to plants. Under certain conditions these slow-release materials result in more efficient use by growing plants. Urea in a slow-release form is popular for use on golf courses, parks, and other special lawn situations. 1.1.6.2 Industrial use Urea has the ability to form 'loose compounds', called clathrates, with many organic compounds. The organic compounds are held in channels formed by interpenetrating helices comprising of hydrogen-bonded urea molecules. This behaviour can be used to separate mixtures, and has been used in the production of aviation fuel and lubricating oils. As the helices are interconnected, all helices in a crystal must have the same 'handedness'. This is determined when the crystal is nucleated and can thus be forced by seeding. This property has been used to separate racemic mixtures. 1.1.6.3 Further commercial uses A stabilizer in nitrocellulose explosives Comprehensive design project 8
Chapter 01
A reactant in the NOx-reducing SNCR and SCR reactions in exhaust gases from combustion, for example, from power plants and diesel engines A component of fertilizer and animal feed, providing a relatively cheap source of nitrogen to promote growth A raw material for the manufacture of plastics, to be specific, urea-formaldehyde resin A raw material for the manufacture of various glues (urea-formaldehyde or ureamelamine-formaldehyde); the latter is waterproof and is used for marine plywood An alternative to rock salt in the de-icing of roadways and runways; it does not promote metal corrosion to the extent that salt does An additive ingredient in cigarettes, designed to enhance flavour A browning agent in factory-produced pretzels An ingredient in some hair conditioners, facial cleansers, bath oils, and lotions A reactant in some ready-to-use cold compresses for first-aid use, due to the endothermic reaction it creates when mixed with water A cloud seeding agent, along with salts, to expedite the condensation of water in clouds, producing precipitation An ingredient used in the past to separate paraffins, due to the ability of urea to form clathrates (also called host-guest complexes, inclusion compounds, and adducts) A flame-proofing agent (commonly used in dry chemical fire extinguishers as Ureapotassium bicarbonate) An ingredient in many tooth whitening products A cream to soften the skin, especially cracked skin on the bottom of one's feet An ingredient in dish soap. To make potassium cyanate A melt agent used in re-surfacing snowboarding halfpipes and terrain park features A raw material for melamine production More than 95% of all melamine production is based on urea. Stamicarbons parent company DSM is the largest melamine producer in the world. A supplementary substitute protein source in feedstuffs for cattle and other ruminants. Because of the activity of micro-organisms in their cud, ruminants are able to metabolize certain nitrogen containing compounds, including urea, as protein substitutes. In the USA this capability is exploited on a large scale. Western Europe, in contrast, uses little urea in cattle feed.
Chapter 01
Feed for hydrolyzation into ammonia which in turn is used to reduce emissions from power plants and combustion engines. Other, miscellaneous products such as de-icing material for airport runways. Although on a smaller scale than as a fertilizer or as raw material for synthetic resins, urea is also used as a raw material or auxiliary material in the pharmaceutical industry, the fermenting and rewing industries and in the petroleum industry. 1.1.6.4 Laboratory use Urea is a powerful protein denaturant. This property can be exploited to increase the solubility of some proteins. For this application, it is used in concentrations up to 10 M. Urea is used to effectively disrupt the noncovalent bonds in proteins. Urea is an ingredient in the synthesis of urea nitrate. Urea nitrate is also a high explosive very similar to ammonium nitrate, however it may even be more powerful because of its complexity. 1.1.6.5 Medical use 1.1.6.5.1 Drug use Urea is used in topical dermatological products to promote rehydration of the skin. If covered by an occlusive dressing, 40% urea preparations may also be used for nonsurgical debridement of nails. This drug is also used as an earwax removal aid. Like saline, urea injection is used to perform abortions. It is also the main component of an alternative medicinal treatment referred to as urine therapy. 1.1.6.5.2 Diagnostic use Isotopically-labeled urea (carbon-14 - radioactive, or carbon-13 - stable isotope) is used in the urea breath test, which is used to detect the presence of the bacteria Helicobacter pylori (H. pylori) in the stomach and duodenum of humans. The test detects the characteristic enzyme urease, produced by H. pylori, by a reaction that produces ammonia from urea. This increases the pH (reduces acidity) of the stomach environment around the bacteria. Similar bacteria species to H. pylori can be identified by the same test in animals such as apes, dogs, and cats . 1.1.6.6 Textile use Urea is a raw material for urea-formaldehyde resins production in the adhesives and textile industries. A significant portion of urea production is used in the preparation of ureaComprehensive design project 10
Chapter 01
formaldehyde resins. These synthetic resins are used in the manufacture of adhesives, moulding powders, varnishes and foams. They are also used for impregnating paper, textiles and leather. In textile laboratories they are frequently used both in dyeing and printing as an important auxiliary, which provides solubility to the bath and retains some moisture required for the dyeing or printing process.
Figure 1.2 (a) The change in world consumption (million metric tons of N) of total synthetic nitrogen fertilizers (solid line) and urea consumption (solid bars) since 1960. Data for 2005 2020 (shown as the shaded region) are calculated assuming an annual increase of 3% in total consumption and 5% in the fraction that is urea. (b) Same data as in panel (a) with the fraction that is urea displayed as a percentage of the total nitrogen fertilizer. Urea is processed into granules or other forms. Urea production is energy intensive. Most commonly, it is produced using natural gas, so the major producing regions are those where natural gas is abundant. Several leading manufacturing countries for urea are Russia, Canada, and Saudi Arabia, but other Middle East producers, including Iran and Iraq are (or were before the Gulf Wars) significant. In the US, urea production facilities are located mainly in the Gulf of Mexico states. Comprehensive design project 11
Chapter 01
Production of urea has at least doubled every decade since 1980 in the Middle East, increasing from 2 million metric tons per year in 1980 to 10 million metric tons year per in 2000. Further expansion of production is anticipated in the coming years in Kuwait, Qatar, Egypt, Oman and Iran. From the mid-1970s to the early 1990s, Russia (USSR) erected at least 40 new ammonia and urea production facilities. Production of urea in China tripled from 1989 to 1999. Dramatic increases in global production have also occurred in many countries since 2000, with several Latin American countries increasing production by more than 25%. As late as the 1960s, urea represented only about 5% of world nitrogen fertilizer use. However, urea usage escalated in the 1980s, such that it represented about 40% of global nitrogen fertilizer by the early 1990s, and soon thereafter urea surpassed ammonium nitrate as the most common nitrogen fertilizer. It is now estimated that urea represents >50% of world nitrogen fertilizer (Figure 1b). Assuming urea consumption continues at 5% per year, as projected for many parts of the world, urea consumption may reach 70% of total nitrogen use by the end of the next decade (Figure 1b): this is a dramatic global change in the composition of nitrogen applied to land throughout the globe. Such projections depend on global commodity markets, construction of new plants, and other factors that are difficult to project, but most of this increase is expected to occur in developing countries, particularly in Asia and Latin America. China and India together account for about half of the global consumption, and have at least doubled their consumption of urea in the past decade. In India, Bangladesh and Pakistan, urea fertilizer has been heavily subsidized (as much as 50% of the cost of production) leading to its widespread use and overapplication. The US and Canada now represent about 20% of the global urea market, with urea constituting about 30% of US synthetic nitrogen fertilizer usage. Consumption is increasing even in regions where land applications of nitrogen have heretofore been low. The rural Canadian provinces of Manitoba, Saskatchewan and Alberta, for example, are now the regions where over 70% of Canadas urea is consumed. Urea is the only form of fertilizer used in British Columbia forests. In Latin America, consumption of urea has fluctuated more than in Asia during the past decade due to various economic crises and unstable political environments, leading to fluctuating incentives and subsidies. This global trend in increased urea consumption represents both a net increase in total nitrogen applied, as well as a shift from the use of nitrate or anhydrous ammonium to urea. These increases parallel the increases in the production of both cereal and meat (associated with increasing human population) that have occurred globally in the past several decades. Urea is used in the production of virtually all crops from corn to Christmas trees, sugar cane to sweet Comprehensive design project 12
Chapter 01
potatoes, and vegetables to vineyards. Urea is preferable to nitrate for growing rice in flooded soils, and thus the Far East and the Mid-East are major consumers of urea. In coated form, urea becomes a slow-release fertilizer and this is one of the most popular forms for applications to lawns, golf courses, and parks, as well as many crops. The global shift toward the use of urea fertilizer stems from several advantages it has over other fertilizer forms. It is less explosive than ammonium and nitrate when stored, it can be applied as a liquid or solid, and it is more stable and cost effective to transport than other forms of reactive nitrogen. The increasing production of granular urea has contributed to its widespread use, as this is safe and easy to transport. Urea also contains twice the nitrogen of ammonium sulfate, making application rates per unit of fertilizer less costly for individual farmers. With the growth of large, industrial farms, the economics and safety of urea transport and storage are thus major factors in the shift away from ammonium nitrate.
Figure 1.3: Global distribution of the consumption of urea fertilizer, in metric tons per year by country, in 1960 (upper panel) and in 1999 (lower panel), based on data from the Global Fertilizer Industry data base (FAO 2001),These estimates of urea consumption do not include uses other than fertilizer.
Chapter 01
Chapter 01
In addition to the direct applications of urea to land and sea, urea is used in many other applications, including manufacture of a wide range of common materials such as urea formaldehyde and plastics. This use represents about 50% of the non-fertilizer urea. Urea is also an additive in fire retardant paints, tobacco products, and in some wines. In the cosmetics industry, urea is an ingredient in moisturizing creams. There are numerous uses of urea in holistic medicine therapies. One application currently being considered which would greatly expand the global use of urea is as a reductant in catalytic and non-catalytic reduction of combustion products in vehicles.
1991 $151
1992 $123
1993 $ 94
1994 $131
1995 $194
1996 $187
1997 $128
Chapter 01
exchange around Rs. 200 million. In 1982 the annual savings of State Fertilizer Corporation stood at Rs.750 million. Urea plant was closed in January 1987. According to the Sri Lanka Custom data records, following graphs shows total urea imports to the country within past 10 years and relative costs involved.
TOTAL UREA IMPORTS
350000 300000
Quantity (MT)
250000 200000 150000 100000 50000 0 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 Year
UREA IMPORTS
Total Cost in Rs Millions
14000 12000 10000 8000 6000 4000 2000 0 1997 1999 2000 2001 2002 2004 2005 2006 2007 Year Figure 1.4 Urea import data
With the development in agriculture sector under present government policies and considering global food crisis, urea demand will further increase in spite there is a concern to use organic fertilizers such as compost instead of urea. Urea is being used as the main fertilizer for paddy as well as for other crops. Excessive applying of urea without considering the requirement has damage water bodies in some part of Sri Lanka. Comprehensive design project 16
Chapter 02
CHAPTER 2
PROCESS SELECTION AND ECONOMIC ASPECTS
Chapter 02
Chapter 02
Chapter 02
Static Equipment Reactor: Reactor is the largest and heaviest key equipment in the urea plant. This is the place where Ammonia and Carbon di-oxide react together. The performance of the reactor influences the performance of the whole urea plant. The size of the shell depends upon the size of plant. For a plant of 2000 tons capacity the height of the shell will be around 30 Meters and Dia around 3 meters.
Stripper Stripper is also a key component where the excess ammonia is separated.
HP Rotating Machines CO2 Compressors This is the largest and most critical rotating equipment. Very large compressors are used of approximate capacities of around 30,000 N cubic meter/hour capacity
HP Ammonia pumps and Carbomate pumps piping Stainless steel 316 L pipes are utilized
HP Control Valves Various control valves are required. The most critical is the solution feed control valve from the reactor to stripper. The material is stainless steel Comprehensive design project 20
Chapter 02
2.2.1.2 Conventional Recycle Process Here all of the non converted ammonia and carbon dioxide were recycled to the urea reactor. In first generation of this process the recirculation of non converted NH 3 and CO2 was performed in two stage. The first recirculation was operated at medium pressure (18-25 bar); the second at low pressure (2-5 bar). The first recirculation comprises at least a decomposition heater, in which carbamate decompose into gaseous NH3 and CO2, and while excess NH3 evaporate simultaneously. The off gas from this first decomposition step was subjected to rectification, from which relatively pure ammonia at the top and a bottom product consisting of an aqueous ammonium carbamate solution were obtained. Both products are recycled separately to the urea reactor. In these processes, all non converted CO 2 was recycled as associated water recycle. Because of the detrimental effect of water on reaction conversion, achieving a minimum CO2 recycle so achieve maximum CO2 conversion was more important than achieving a low NH3 recycle. All conventional processes therefore typically operate at high NH 3:CO2 ratios (4-5 Comprehensive design project 21
Chapter 02
mol/mol) to maximize CO2 conversion per pass. Although some of these conventional processes partly equipped with ingenious heat exchanging net works have survived until now. Their importance decreased rapidly as the so-called stripping process was developed.
Chapter 02
Chapter 02
Chapter 02
synthesis section are also minimized, and no separate ammonia recycle is required. The urea solution coming from the recirculation stage contains about 75 wt% urea. This solution is concentrated in the evaporation section. If the process is combined with a prilling tower for final product shaping, the final moisture content of urea from the evaporation section is 0.25 wt%. If the process is combined with a granular unit, the final moisture content may wary from 1 to 5 wt%, depending on granulation requirements. Higher moisture content can be realized in a single stage evaporator; where as low moisture content are economically achieved in a two stage evaporation section. When urea with an extremely low biuret content is required ( at maximum of 0.3 wt%) pure urea crystals are produced in a crystallization section. These crystals are separated from the mother liquor by combination of sieve bends and centrifuges and are melted prior to final shaping in a prilling tower or granulation unit. The process condensate emanating from water evaporation from the evaporation or crystallization sections contains ammonia and urea. Before this process condensate is purged, urea is hydrolyzed into ammonia and carbon dioxide, which are stripped off with steam and return to urea synthesis via the recirculation section. This process condensate treatment section can produce water with high purity, thus transforming this waste water treatment into the production unit of a valuable process condensate, suitable for, e.g., cooling tower or boiler feed water makeup. Since the introduction of the Stamicarbon CO2 stripping process, some 125 units have been built according to this process all over the world.
Chapter 02
Comprehensive design project Figure 2.2 CO2 stripping process flow diagram 26
Chapter 02
Chapter 02
The urea solution from the medium pressure decomposer is subjected to a second low pressure decomposition step. Here further decomposition of ammonium carbamate is achieved, so that a substantially carbamate free aqueous urea solution is obtained. Off gas from this low pressure decomposer is condensed and recycled as an aqueous ammonium carbamate solution to the synthesis section via the medium pressure recovery section. Concentrating the urea water mixture obtained from the low pressure decomposer is preformed in a single or double evaporator depending on the requirement of the finishing section. Typically, if prilling is chosen as the final shaping procedure, a two stage evaporator is required, whereas in the case of a fluidized bed granulator a single evaporation step is sufficient to achieve the required final moisture content of the urea melt. In some versions of the process, heat exchange is applied between the off gas from the medium pressure decomposer and the aqueous urea solution to the evaporation section. In this way, the consumption of low pressure steam by the process is reduced. The process condensate obtained from the evaporation section is subjected to a desorption hydrolysis operation to recover the urea and ammonia contained in the process condensate.
Chapter 02
. Disadvantages Large quantity of ammonia salt is formed as co product Overall carbon dioxide conversion is low. High production cost High energy cost High environment pollution
High purity
Urea Manufacturing Plant Snamprogetti Ammonia and self stripping processes Isobaric double recycle process ACES process Low production cost High energy recovery Low environment pollution High efficiency Low consumption of low pressure steam
Among above urea manufacturing processes, ACES process is selected because of it has following advantages compared to other processes
Chapter 03
CHAPTER 3
PROCESS DESCRIPTION AND FLOW SHEET
Chapter 03
Chapter 03
The reactor is operated at 1900C and an NH3:CO2 molar feed ratio of 4:1. Liquid ammonia is fed directly to the reactor, whereas gaseous carbon dioxide after compression is introduced into the bottom of the stripper as a stripping aid. The synthesis mixture from the reactor, consisting of urea, unconverted ammonium carbamate, excess ammonia, and water, is fed to the top of the stripper. The stripper has two functions. Its upper part is equipped with trays where excess ammonia is partly separated from the stripper feed by direct countercurrent contact of the feed solution with the gas coming from the lower part of the stripper. This pre stripping in the top is said to be required to achieve effective CO 2 stripping in the lower part. In the lower part of the stripper (a falling film heater), ammonium carbamate is decomposed and the resulting CO2 and NH3 as well as the excess NH3 are evaporated by CO2 stripping and steam heating. The overhead gaseous mixture from the top of the stripper is introduced into the carbamate condenser. Here the gaseous mixture is condensed and absorbed by the carbamate solution coming from the medium pressure recovery stage. Heat liberated in the high pressure carbamate condenser is used to generate low pressure steam. The gas and liquid from the carbamate condensers are recycled to the reactor by gravity flow. The urea solution from the stripper, with a typical NH3 content of 15 wt%, is purified further in the subsequent medium and low pressure decomposers, operating at 17.5 and 2.5 bars, respectively. Ammonia and carbon dioxide separated from the urea solution here are recovered through stepwise absorption in the low and medium pressure absorbers. Condensation heat in the medium pressure absorber is transferred directly to the aqueous urea solution feed in the final concentration section; the purified urea solution is concentrated further either by two stage evaporation up to 99.7 % for urea prill production or by a single evaporation 98.5 % for urea granule production. Water vapour formed in the final concentrating section is condensed in surface condensers to form process condensate. Part of this condensate is used as an absorbent in the recovery sections, where as remainder is purified in the process condensate treatment section by hydrolysis and steam stripping, before being discharge from the urea plant. The highly concentrated urea solution is finally processed either through the prilling tower or via the urea granulator. Instead of concentration via evaporation, the ACES process can also be combined with a crystallization section to produce urea with low biuret content.
Chapter 03
3.2.2 Stripper
Carbon dioxide is introduced into the bottom of the stripper as a stripping aid. The synthesis mixture from the reactor, consisting of urea, unconverted ammonium carbamate, excess ammonia, and water, is fed to the top of the stripper. Medium pressure steam is supplied to the stripper. The stripper has two functions. Its upper part is equipped with trays where excess ammonia is partly separated from the stripper feed by direct countercurrent contact of the feed solution with the gas coming from the lower part of the stripper. This pre stripping in the top is said to be required to achieve effective CO2 stripping in the lower part. In the lower part of the stripper (a falling film heater), ammonium carbamate is decomposed and the resulting CO 2 and NH3 as well as the excess NH3 are evaporated by CO2 stripping and steam heating. The overhead gaseous mixture from the top of the stripper is introduced into the carbamate condenser. Following reaction occurs inside the stripper. Comprehensive design project 34
Urea Manufacturing Plant NH2COONH4 + heat 2NH3 + CO2 NH3(l) NH3(g) H = +84 kJ/mol
Chapter 03
3.2.4 Scrubber
In the scrubber Ammonia and Carbon Dioxide coming from the reactor are absorbed to ammonia and ammonium carbamate solution which is going to Carbamate Condenser.
Chapter 03
The discharged granules are separated into three sizes, product, small and large size by the screen. Product size granules are further cooled below 60C in the product cooler to be sent to the urea storage or bagging facility. Large size granules are crushed by the crusher. The rushed particles and smaller size particles from the screen are recycled to the granulator as seed.Urea dust contained in the exhaust air from the granulator and the product cooler is scrubbed in the dust scrubber by contacting counter currently with aqueous urea solution. The urea dust content in the exit air of the bag filter is 30 mg/m3 or less. Urea recovered in the bag filter, approximately 2.5-3.5 % of production rate, is recycled to the urea granulator.
Chapter 03
Chapter 04
CHAPTER 4
SITE SELECTION
Chapter 04
Following Facts should be concern regarding site selection Availability of raw material Infrastructure facilities Legal obligations enforced by relevant authority or the government Environment and climate conditions Labour force availability Social considerations Waste management
Chapter 04
Hambanthota is developing area under Mahinda Chinthana concept. Many developing projects are underway. An international sea port is going to be established in hambantota which can handle large ships which are unable to access in the Colombo port. Also infrastructure facilities will be developed along with these projects. Vast amount of land is available for low cost in order to establish the plant closed to Hambantota port. Even if there are no enough qualified employees in Hambantota area, due to rapid development along with good infrastructure facilities it would be easy to attract employees from outside areas. Government welcomes projects related to hambantota area and many benefits can be gain such as reduction in tax, grace periods for loans etc. The government is planning to establish a petroleum refinery in Hambanthota. In Trincomalee much of above mentioned benefits are there, but considering the establishment of petroleum refinery and massive port compared to Trincomalee, Hambantota becomes the more suitable option. It is not economical to import ammonia and carbon dioxide from abroad because of high transportation cost and additional amount of money have to be spend on buying those materials. Those raw materials can be produced at low cost in Sri Lanka. So it is better to have an ammonia plant. Under the governments plan to establish a petroleum refinery in Hambanthota, hydrogen can be gained as a byproduct from petroleum refinery and it can be use as a raw material for ammonia production. So it would be better to have ammonia plant in future to aid urea production.
Chapter 04
Chapter 04
4.2.1 Importance
Plant layout is an important decision as it represents long-term commitment. An ideal plant layout should provide the optimum relationship among output, floor area and manufacturing process. It facilitates the production process, minimizes material handling, time and cost, and allows flexibility of operations, easy production flow, makes economic use of the building, promotes effective utilization of manpower, and provides for employees convenience, safety, comfort at work, maximum exposure to natural light and ventilation. It is also important because it affects the flow of material and processes, labour efficiency, supervision and control, use of space and expansion possibilities etc.
An efficient plant layout is one that can be instrumental in achieving the Following objectives: a) Proper and efficient utilization of available floor space b) To ensure that work proceeds from one point to another point without any delay c) Provide enough production capacity. d) Reduce material handling costs e) Reduce hazards to personnel f) Utilize labour efficiently Comprehensive design project 43
Urea Manufacturing Plant g) Increase employee morale h) Reduce accidents i) Provide for volume and product flexibility j) Provide ease of supervision and control k) Provide for employee safety and health l) Allow ease of maintenance m) Allow high machine or equipment utilization n) Improve productivity
Chapter 04
Chapter 04
Ammonia releases from urea plants Early nineteen eighties 8 kg NH3/mt final product Presently 0.7 kg NH3/mt final product
Table 4.1 Ammonia releases from urea plants Not only ammonia, carbon dioxide and urea releases from process plants have a negative influence on the environment but also the unnecessary use of energy is negative from an environmental point of view and from the economic point of view as well. Following table shows the present typical energy consumption for urea production
Typical consumption figures for a granulation plant Steam (22 bar, 330oC) Steam (4 bar saturated) (production) Electricity (including granulation section) 805 kg/mt urea -415 kg/mt urea 50 kWh/mt urea
Cooling water (including granulation section) 58 mt/mt urea Table 4.2 Typical consumption figures for a granulation plant Emissions from Urea manufacturing process are listed below. Emission Media Substance Ammonia Formaldehyde Methanol Total Nitrogen Particulate Matter (PM10) Volatile Organic Compounds(VOCs) To Atmosphere To Water Via Solid Waste
Table 4.3 Emissions from Urea manufacturing process Comprehensive design project 45
Chapter 04
Chapter 04
In general, there are four types of emission estimation techniques (EETs) that may be used to estimate emissions from the facility. The four types are: Sampling or direct measurement; Mass balance; Fuel analysis or other engineering calculations; and Emission factors
N/C ratio meter in the Synthesis section Instead of using a gaschromatograph or a mass spectrometer in the gas phase of the synthesis section, Nitrogen/Carbon (N/C) ratio meters are installed in the liquid phase (reactor liquid outlet) of the urea synthesis section The principle of this N/C meter is based on the linear relationship between liquid density and the N/C ratio. The density is measured continuously with a solartron meter, being an instrument in which vibrations are measured in an extremely accurate way whereby the vibrations are a measure of the density of the reactor liquid. This N/C ratio meter allows the process at all times to be operated at the optimum ratio to achieve highest reactor efficiency combined with higher energy efficiency. Special procedures are used to eliminate emissions during start-up.
Urea plant waste water treatment section The process water in urea plants contains ammonia, carbon dioxide and urea. The concentrations of these components vary within a range depending on the operating conditions, On average, the concentrations in the process water are about 6 wt.% ammonia, 4 wt.% carbon dioxide and 1 wt.% urea.
Urea Manufacturing Plant Sources of the ammonia and urea are Condensate from the evaporators.
Chapter 04
Off-gases from the recirculation section, which are absorbed in the process water. Off-gases from the synthesis section, which are absorbed in the process water. Flush and purge water for pumps. Liquid drains. The purpose of the process water treatment is to remove ammonia, carbon dioxide and urea from the process condensate. For every tonne of urea produced, approximately 0.3 tonnes of water are formed. This water is usually discharged from the urea concentration and evaporation section of the plant. Removal of ammonia and urea from wastewaters can be a problem as it is difficult to remove one in the presence of the other. One method used to overcome this problem is the hydrolysis of urea to ammonium carbamate, which is decomposed to ammonia and carbon dioxide. These gases can then be stripped from the wastewaters. Urea plants are in operation that produces wastewaters with ammonia and urea levels below 1ppm. This water can then be used for a variety of purposes depending on the required quality such as cooling water or Boiling Feed Water make-up. The recovered ammonia and carbon dioxide are returned to the process to be subsequently converted into urea.
Absorbers Absorbers are used in urea plant to eliminate emissions to the atmosphere, can be classified as follows: (1) The vent from the synthesis section of the plant The purge from the urea synthesis section contains inerts, ammonia and carbon dioxide. To avoid ammonia emissions from this purge a low pressure absorber is installed in purge stream. First the ammonia is washed out with a large flow of low concentrated and cooled process water and secondly the remaining ammonia is absorbed in cooled condensate or clean waste water. (2) The vent from the low pressure section of the plant The ammonia and carbon dioxide present in the off gases of the recirculation section, the Process Water Treatment System and the evaporation section are washed out in an atmospheric absorber where large amounts of cooled low concentrated process water are used to absorb all the ammonia present in said off gases.
Chapter 04
Because of the present low releases during steady state operation in urea manufacturing the consideration regarding environmental issues has changed towards further reducing of effluents and emissions from non-continuous sources during non-steady state conditions such as start-up and shut-down situations. A change in the start-up procedure of the urea synthesis section has reduced the impact on the environment considerably. Presently the ability to measure the feed flows (NH3 and CO2) very accurate in combination with the ability to measure the N/C ratio have enabled us to feed the synthesis section from the very beginning of the start-up with the correct NH3/CO2 ratio, thus eliminating the need, during the initial stage of start-up, to vent excess CO2 accompanied by some NH3 into the atmosphere. Special shut-down and draining facilities assure that non converted NH 3 and CO2 are recovered by the process after a shut-down. To achieve this facility to feed clean water to dilute the carbamate formed from non converted NH3 and CO2 from the synthesis section has been introduced. The dilution should be to the extent that no ammonia will escape from the liquid under atmospheric pressure. The water is in principle introduced in the low pressure carbamate condenser and subsequently cooled to increase absorption capacity, and drained in the ammonia water tank. After restart of the plant the NH3 and CO2 in this tank are recovered via the waste water treatment section. The clean water used for the dilution may be an amount of clean waste water stored for such purpose. In case sufficient condensate is available in the complex no such additional storage of clean waste water is required and condensate may be used as well.
Chapter 04
Flash point: Not applicable Flammability limits: Not applicable Auto-ignition temperature: Not applicable The substance decomposes on heating above melting point, producing toxic gases, and reacts violently with strong oxidants, nitrites, inorganic chlorides, chlorites and perchlorates, causing fire and explosion hazard
Hazard identification Classified as hazardous chemical according to criteria in the HS (Minimum Degrees of Hazard) Regulations 2001 Route of entry and health hazards Harmful if swallowed. - It may cause irritation Harmful if inhaled. Causes serious eye irritation. Harmful to terrestrial vertebrates.
Inhalation: Slight irritant. Elevated exposure may result in mucous membrane irritation (nose & throat). may cause nausea, vomiting, diarrhea and GI irritation. Skin: Irritant. Prolonged contact may result in irritation, itching and possible skin rash. Eyes: Irritant. May cause lachrymation, irritation, pain & redness Ingestion: Has diuretic effect. Ingestion of large quantities may lead to nausea and vomiting.
No adverse health effects expected under normal conditions. Urea can be irritating to skin and eyes.Too high concentrations in the blood can cause damage to organs of the body. Low concentrations of urea such as in urine are not dangerous. It has been found that urea can cause Comprehensive design project 50
Chapter 04
algal blooms to produce toxins, and urea in runoff from fertilizers may play a role in the increase of toxic blooms.
First aid (Emergency procedure) In the event of an emergency, remove the victim from further exposure, send for medical assistance, and initiate the following emergency procedures: Skin Wash exposed area with soap and water. If irritation persists, get medical attention as soon as possible. Eyes Wash eyes with plenty of water for at least 15 minutes, lifting lids occasionally. Seek Medical Aid. Inhalation Remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen Ingestion If swallowed, induce vomiting immediately after giving two glasses of water. Never give anything by mouth to an unconscious person. Fire Extinguisher Any means suitable for extinguishing surrounding fire. Fire extinguisher should available in any risky places in the plant. Extinguishing media: CO2, foam, dry powder, water
Handling & Storage Precautionary Statements Keep out of reach of children. Avoid breathing vapors, or dusts. Wash hands thoroughly after handling. Do not eat drink or smoke when using this product. Avoid unintended release to the environment. Use with adequate ventilation. Avoid contact with eyes, skin, and clothes.
Urea Manufacturing Plant Safe Handling Avoid generating dusts. Use only outdoors or in a well-ventilated area. Storage
Chapter 04
Store in sealed containers in cool, dry, well ventilated place away from incompatible materials. Wash thoroughly after handling. Keep container closed. Transportation No special transport requirements necessary Environmental Exposure Limit (EEL): Not assigned Avoid washing excessive amounts into streams and waterways.
Exposure Controls & Personal Protection Exposure Standards Workplace Exposure Standards (WES): Particulates not otherwise classified Inspirable dust 10mg/m3 Respirable dust 3mg/m3 Personal Protective Equipment Respiratory: If dusts particles are present wear suitable dust mask. Eyes/Face: Safety glasses. If dusts present wear goggles. Skin: use Overalls and gloves.
Eye wash facilities should be available. Wash hands after working with substance. Collect and place in clean sealable containers. Avoid generating dusts.
Engineering Controls Ventilation: Use in well ventilated area. If dusts are generated use local extraction to control
Disposal Considerations Observe local authority restrictions that may apply. Collection into sealable containers and dispose of in an approved land fill. If practicable apply excess fertilizer at recommended rates to appropriate land. Rinse containers thoroughly prior to re-use. Otherwise render unusable, and dispose of as waste. Comprehensive design project 52
Chapter 04
Hazard identification Irritating or corrosive to exposed tissues. Inhalation of vapors may result in pulmonary edema and chemical pneumonitis
Route of entry and health hazards Harmful if contact with eye Harmful if inhaled. Irritant if contact with skin and eye
Eye effects Mild concentrations of product will cause conjunctivitis. Contact with higher concentrations of product will cause swelling of the eyes and lesions with a possible loss of vision.
Chapter 04
Exposure to 50 ppm or less for 5 minutes was not considered irritating by volunteers, while exposure to 72 ppm was irritating to a few individuals and 134 ppm was irritating and caused tearing. At 700 ppm, the gas is immediately and severely irritating. Direct contact with the liquefied gas can cause frostbite and corrosive injury to eye. Permanent eye damage or blindness could result. Severe, permanent eye injury, including an almost complete loss of vision, has been reported following direct contact with liquefied ammonia gas. Skin effects Mild concentrations of product will cause dermatitis or conjunctivitis. Contact with higher concentrations of product will cause caustic-like dermal burns and inflammation. Toxic level exposure may cause skin lesions resulting in early necrosis and scarring. High levels of airborne ammonia gas dissolve in moisture on the skin, forming corrosive ammonium hydroxide. At 10000 ppm, ammonia is mildly irritating to moist skin. At 20000 ppm, the effects are more pronounced and 30000 ppm may produce chemical burns with blistering. These same exposure levels would be almost certainly fatal due to inhalation health effects. Direct contact with liquefied gas can cause frostbite and corrosive burns. Symptoms of mild frostbite include numbness, prickling and itching in the affected area. Symptoms of more severe frostbite include a burning sensation and stiffness of the affected area. The skin may become waxy white or yellow. Blistering, tissue death and gangrene may also develop in severe cases. Corrosive burns of the skin have resulted from direct contact with a jet of liquefied ammonia. Permanent scarring of the skin may result. Ingestion effects Since product is a gas at room temperature, ingestion is unlikely.
Inhalation effects Corrosive and irritating to the upper respiratory system and all mucous type tissue. Depending on the concentration inhaled, it may cause burning sensations, coughing, wheezing, shortness of breath, headache, nausea, with eventual collapse. Toxic effects to the respiratory system, senses, liver, kidneys and bladder observed in mammalian species from prolonged inhalation exposures at above 100 ppm Inhalation of excessive amounts affects the upper airway (larynx and bronchi) by causing caustic-like burning Comprehensive design project 54
Chapter 04
resulting in edema and chemical pneumonitis. If it enters the deep lung, pulmonary edema will result. Pulmonary edema and chemical pneumonitis are potentially fatal conditions.
Long term health effects of exposure to Ammonia gas No significant differences in lung function were observed in workers exposed to 9.2 ppm ammonia for an average of 12.2 years compared to controls with very low exposure (less than 1 ppm). No conclusions can be drawn from one case report which described lung injury following long-term exposure to ammonia because the person was a long-term smoker. People with repeated exposure to ammonia may develop a tolerance (or acclimatization) to the irritating effects after a few weeks.
First aid (Emergency procedure) Eyes Flush contaminated eye(s) with copious quantities of water. Part eyelids to assure complete flushing. Continue for a minimum of 15 minutes. Persons with potential exposure to ammonia should not wear contact lenses. Skin Remove contaminated clothing as rapidly as possible. Flush affected area with copious quantities of water. In cases of frostbite or cryogenic "burns" flush area with lukewarm water. Do not use hot water. A physician should see the patient promptly if the cryogenic "burn" has resulted in blistering of the dermal surface or deep tissue freezing. Ingestion Not specified. Seek immediate medical attention. Inhalation Prompt medical attention is mandatory in all cases of overexposure. Rescue personnel should be equipped with self-contained breating apparatus. Conscious persons should be assisted to an uncontaminated area and inhale fresh air. Quick removal from the contaminated area is most important. Unconscious persons should be moved to an uncontaminated area, given mouth-to-mouth resuscitation and supplemental oxygen. Keep victim warm and quiet. Assure that mucus or vomited material does not obstruct the airway by positional drainage.
Urea Manufacturing Plant Fire Extinguisher Extinguisher media Water fog, foam. Use media suitable for surrounding fire. Fire extinguished instruction
Chapter 04
If possible, stop the flow of gas. Since ammonia is soluble in water, it is the best extinguishing media not only in extinguishing the fire, but also absorbing the escaped ammonia gas. Use water spray to cool surrounding containers.
Handling & Storage Earth-ground and bond all lines and equipment associated with the ammonia system. Electrical equipment should be non-sparking or explosion proof. Gaseous or liquid anhydrous ammonia corrodes certain metals at ambient temperatures. The presence of oxygen enhances the corrosion of ordinary or semialloy steels. The addition of water inhibits this enhancement. Keep anhydrous ammonia systems scrupulously dry. Use only in well-ventilated areas. Valve protection caps must remain in place unless container is secured with valve outlet piped to use point. Do not drag, slide or roll cylinders. Use a suitable hand truck for cylinder movement. Use a pressure regulator when connecting cylinder to lower pressure (<500 psig) piping or systems. Do not heat cylinder by any means to increase the discharge rate of product from the cylinder. Use a check valve to trap in the discharge line to prevent hazardous back flow into the cylinder. Protect cylinders from physical damage. Store in cool, dry, well-ventilated area away from heavily trafficked areas and emergency exits. Do not allow the temperature where cylinders are stored to exceed 125oF (52oC). Cylinders should be stored upright and firmly secured to prevent falling or being knocked over. Full and empty cylinders should be segregated. Use a "first in-first out" inventory system to prevent full cylinders from being stored for excessive periods of time. Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in an enclosed space such as a car trunk, van or station wagon. A leak can result in a fire, explosion, asphyxiation or a toxic exposure.
Chapter 04
Use local exhaust ventilation to reduce concentrations to within current exposure limits. A laboratory type hood is suitable for handling small or limited quantities.
Personal protection Eye/face protection Gas tight chemical goggles or full-face piece respirator. Skin protection Protective gloves made of any suitable material. Respiration protection Respiratory protection with full face piece or self-contained breathing apparatus should be available for emergency use. Air purifying respirators must be equipped with suitable cartridges. Do not exceed maximum use concentrations. Do not use air purifying respirators in oxygen deficient/immediately dangerous to life and health (IDLH) atmosphere. Consult manufacturers instructions before use. Other general protections Safety shoes, safety shower, eyewash "fountain".
Disposal Considerations Do not attempt to dispose of residual waste or unused quantities. Return in the shipping container properly labeled, with any valve outlet plugs or caps secured and valve protection cap in place to BOC Gases or authorized distributor for proper disposal.
Incompatible materials Strong acids. Ammonium carbamate reacts with chlorine, bromine, mercury, silver and hypochlorite to form explosive compounds.
Chapter 04
Ammonia vapors in the range of 16% to 25% by volume in air can explode on contact with an ignition source. The use of welding or flame cutting equipment on process lines is not recommended unless all ammonium carbamate has been removed. Avoid welding in confined space. Flash point: Not applicable Flammability limits: Not applicable Auto-ignition temperature: not applicable
Hazard identification Ammonium carbamate has a potential for acute health effects Eyes and Skins Eyes: Noticeable irritation to the eyes will occur at ammonia concentrations of 100 PPM. Severe irritation to the eyes will occur at concentrations of 400 PPM. Skin: Contact with ammonium carbamate can result in first, second and third degree burns. Inhalation Severe irritation of nose and throat occurs at ammonia concentrations of 400 PPM. Serious coughing and bronchial spasms occur at ammonia concentrations of 1,700 PPM. Less than a thirty minute exposure to ammonia concentrations of 1,700 PPM may be fatal. IDLH at 300 PPM. Ingestion Ingestion may be fatal. May result in first, second or third degree burns.
First aid (Emergency procedure) Eyes Immediately flood with large amounts of water for at least 15 minutes. Seek medical attention. Skin Remove contaminated clothing immediately. Flush the skin with large amounts of water until all material is removed (at least 15 minutes). Wash all contaminated clothing before re-use.
Chapter 04
Do not induce vomiting. Encourage the victim to drink large amounts of water, substituting as available, diluted vinegar, lemon juice or orange juice. Inhalation Use respiratory protection as necessary and remove to fresh air at once. If breathing stops, administer artificial respiration
Fire Extinguisher Extinguisher media: Water Avoid direct streams of water application which may result in chemical exposure due to splashing Fire extinguishing agents to avoid CO2 may react violently. Use water spray to control ammonia vapors. Adding water to ammonium carbamate will generate heat and increase the ammonia vapors generated. Wear full protective clothing with an approved self contained breathing apparatus.
Storage and Handling Provide ventilation sufficient to maintain exposure to ammonia vapors below the permissible exposure limit. Avoid all contact with the body. Minimize gas contact. Employ good maintenance practices to prevent leaks. Keep away from heat and open flames. Use good process control measures to prevent releases. Preferably stored outside. Otherwise in cool, dry well-ventilated non-combustible location away from all ignition sources and oxidizers.
Exposure Controls/Personal Protection Engineering Controls Vessel and drum labels are required on all containers. Personnel training should include adequate inspection techniques on equipment such as pumps, hoses, and valves. Eye Protection Face shield and tight fitting gas tight splash goggles Protective Clothing Chemical resistant suit with rubber or vinyl gloves and rubber boots
Chapter 04
Use a NIOSH/MSHA approved full-face negative pressure respirator fitted with ammonia cartridges for exposures at or below 300 PPM. For concentrations above 300 PPM, use a full-face positive pressure self-contained breathing apparatus Other Protective Clothing or Equipment Provide an eyewash station and safety shower at sites handling or storing Ammonium Carbamate.
Disposal Considerations Product Disposal Disposal of ammonium carbamate may be subject to federal, state and local regulations.
General Comments Handlers of this product should review their operations in terms of applicable laws and regulations, and then consult with appropriate regulatory agencies before discharging or disposing of any waste material.
Flammability Not flammable under normal conditions and may be combustible at high temperature. Auto-Ignition Temperature: Not available. Flash Points: Not available. Flammable Limits: Not available After the combustion products are carbon oxides (CO, CO2), nitrogen oxides (NO, NO2...).
Chapter 04
Hazardous in case of skin contact (irritant), of ingestion, of inhalation. Slightly hazardous in case of skin contact (permeator), of eye contact (irritant). Potential Chronic Health Effects: Hazardous in case of skin contact (irritant), of ingestion, of inhalation. Slightly hazardous in case of skin contact ( permeator ), of eye contact (irritant). No carcinogenic effects No mutagenic effects No teratogenic effects
First aid (Emergency procedure) Eye Check for and remove any contact lenses. In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Cold water may be used. Get medical attention if irritation occurs. Skin In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an emollient. Remove contaminated clothing and shoes. Cold water may be used. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention. Serious Skin Contact Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek medical attention. Inhalation If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention. Ingestion Do not induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. If large quantities of this material are swallowed, call a physician immediately. Loosen tight clothing such as a collar, tie, belt or waistband.
If the contamination is series it should call a doctor immediately Comprehensive design project 61
Urea Manufacturing Plant Fire Extinguisher Small fire: Use dry chemical powder. Large fire: Use water spray, fog or foam. Do not use water jet.
Chapter 04
Handling and storage Keep away from heat. Keep away from sources of ignition. Empty containers pose a fire risk; evaporate the residue under a fume hood. Ground all equipment containing material. Do not breathe dust. Avoid contact with skin. Wear suitable protective clothing. In case of insufficient ventilation, wear suitable respiratory equipment. If you feel unwell, seek medical attention and show the label when possible. Keep container tightly closed. Keep container in a cool, wellventilated area.
Exposure Controls & Personal Protection Engineering Controls Use process enclosures, local exhaust ventilation, or other engineering controls to keep airborne levels below recommended exposure limits. If user operations generate dust, fume or mist, use ventilation to keep exposure to airborne contaminants below the exposure limit.
Personal Protection Ware safety glasses, Lab coat, Dust respirator. Be sure to use an approved/certified respirator or equivalent, Gloves. In large Spill use Splash goggles, Full suit, Dust respirator, Boots, Gloves. A self contained breathing apparatus should be used to avoid inhalation of the product. Suggested protective clothing might not be sufficient; consult a specialist before handling this product.
Chapter 05
CHAPTER 5
MASS BALANCE CALCULATION
Chapter 05
Reactions involved in the process 2NH3 + CO2 NH2COONH4 + heat Sch Mass Wt% 2 34 0.4359 1 44 0.5641 1 78 1.0000
NH2COONH4 + heat NH2CONH2 + H2O Sch: Mass Wt% 1 78 1.0000 1 60 0.7692 1 18 0.2308
Chapter 05
0.4359 0.5641
Chapter 05
5.1.1 Reactor
Weight MT/day 32.4 37.2 190 175
Wt % 87.21% MT C bar Weight MT/day 263.3 263.3 170 175 Weight MT/day 486.1
4.8 12.79%
Wt % 23.76%
1559.7 76.24% 2045.9 MT/day 170 C 175 bar Weight MT/day Wt % 1060.0 36.90% 591.0 20.57% 903.6 31.46% 318.0 11.07% 2872.6 MT/day 190 C 175 bar
Component Urea Carbamate Component NH3 Flow rate Temperature Pressure Weight MT/day 600.7 600.7 170 175 Wt % 100.00% MT/day C bar NH3 H2O Flow rate Temperature Pressure
Chapter 05
5.1.2 Stripper
Component Component Urea Carbamate NH3 H2O Flow rate Temperature Pressure Weight MT/day Wt % 1060.0 36.90% 591.0 20.57% 903.6 31.46% 318.0 11.07% 2872.6 MT/day 190 C 175 bar NH3 CO2 Flow rate Temperature Pressure
Weight MT/day
Wt %
MP STEAM COND.
Component Urea Carbamate Wt % 100.00% MT C bar NH3 H2O Flow rate Temperature Pressure
Weight MT/day Wt % 1060.0 48.00% 499.1 22.60% 331.3 15.00% 318.0 14.40% 2208.3 MT/day 178 C 175 bar
Chapter 05
Component Component NH3 CO2 Carbamate Flow rate Temperature Pressure Weight MT/day 56.4 Wt % 26.89% NH3 CO2 Flow rate Temperature Pressure
Weight MT/day
Wt %
STM
Weight MT/day
Wt %
SC
Wt %
Chapter 05
5.1.4 Scrubber
Weight MT/day Wt % 1.4 12.79% 9.7 87.21% 11.2 MT/day 189 C 175 bar
Component Component NH3 CO2 Flow rate Temperature Pressure Weight MT/day 32.4 37.2 190 175 NH3 Wt % 87.21% MT C bar CO2 Carbamate Flow rate Temperature Pressure
Weight MT/day Wt % 56.4 26.89% 22.7 10.82% 130.7 62.29% 209.8 MT/day 153 C 175 bar
4.8 12.79%
Chapter 05
Weight MT/day Wt % 327.3 79.49% 84.5 20.51% 411.7 MT/day 157 C 17.5 bar
Weight MT/day Wt % 1060.0 48.00% 499.1 22.60% 331.3 15.00% 318.0 14.40% 2208.3 MT/day 178 C 175 bar Component Urea Carbamate NH3 H2O Flow rate Temperature Pressure
Weight MT/day Wt % 1060 59.00% 349.4 19.45% 69.3 3.85% 318.0 17.70% 1796.6 MT/day 157 C 17.5 bar
Chapter 05
Weight MT/day Wt % 1060 59.00% 349.4 19.45% 69.3 3.85% 318.0 17.70% 1796.6 MT/day 157 C 17.5 bar
Weight MT/day Wt % 221.5 44.67% 274.4 55.33% 495.9 MT/day 129 C 2.5 bar
Component Urea Wt % 100.00% MT C bar H2O NH3 Flow rate Temperature Pressure
Weight MT/day Wt % 1060.6 75.81% 338.0 24.16% 0.5 0.04% 1399.1 MT/day 129 C 2.5 bar
Chapter 05
Weight MT/day Wt % 221.5 44.67% 274.4 55.33% 495.9 MT/day 129 C 2.5 bar
CW
Weight MT/day Wt % 9.5 1.91% 486.4 98.09% 495.9 MT/day 129 C 1.5 bar
Chapter 05
Wt % 77.73%
Weight MT/day Wt % 9.5 1.91% 486.4 98.09% 495.9 MT/day 129 C 17.5 bar
Weight MT/day Wt % 265.4 28.89% 0.0 0.00% 653.4 71.11% 918.8 MT/day 150 C 12 bar
Chapter 05
Weight MT/day Wt % 1060.6 75.81% 338.0 24.16% 0.5 0.04% 1399.1 MT/day 178 C 2.5 bar
Weight MT/day Wt % 1060.3 82.00% 232.4 17.98% 0.3 0.02% 1293.0 MT/day 110 C 0.7 bar
Chapter 05
Weight MT/day Wt % 1060.3 82.00% 232.4 17.98% 0.3 0.02% 1293.0 MT/day 110 C 2 bar
Weight MT/day Wt % 1060.1 93.00% 79.7 6.99% 0.1 0.01% 1139.9 MT/day 110 C 0.7 bar
Chapter 05
Weight MT/day Wt % 1060.1 93.00% 79.7 6.99% 0.1 0.01% 1139.9 MT/day 110 C 2 bar Weight MT/day Wt % 1060.0 99.20% 8.5 0.80% 1068.5 MT/day 112 C 0.8 bar
Chapter 05
Component Component H2O Urea NH3 Flow rate Temperature Pressure Weight MT/day Wt % 105.6 0.3 99.53% 0.28% H2O Urea NH3 Flow rate Temperature Pressure
Component Component H2O Urea NH3 Flow rate Temperature Pressure Weight MT/day Wt % 20.0 0.6 94.79% 2.84% H2O Urea NH3 Flow rate Temperature Pressure
Weight MT/day Wt % 309.5 100.00% 0.0 0.00% 0.0 0.00% 309.5 MT/day 40 C 1 bar
Chapter 05
5.1.13 Granulator
Component Urea H2O Flow rate Temperature Pressure Component Urea H2O Flow rate Temperature Pressure Weight MT/day Wt % 31.8 99.20% 0.3 0.80% 32.1 MT/day 52 C 1.5 bar Weight MT/day Wt % 720.8 99.20% 5.8 0.80% 726.6 MT/day 89 C 1 bar Weight MT/day Wt % 10.6 0.45% 0.1 0.00% 2356.9 99.55% 2367.6 MT/day 55 C 6 bar
GRANULATION SECTION
Weight MT/day Wt % 1060.0 99.20% 8.5 0.80% 1068.5 MT/day 112 C 2 bar
Chapter 05
5.1.14 Screen
Weight MT/day Wt % 1802.0 99.20% 14.5 0.80% 1816.5 MT/day 89.5 C 1 bar Weight MT/day Wt % 477.0 99.20% 3.8 0.80% 480.8 MT/day 89.5 C 1 bar
Weight MT/day Wt % 243.8 99.20% 2.0 0.80% 245.8 MT/day 89.5 C 1 bar
Weight MT/day Wt % 1081.2 99.20% 8.7 0.80% 1089.9 MT/day 89.5 C 1 bar
Chapter 05
Weight MT/day Wt % 21.2 0.34% 0.2 0.00% 6213.6 99.66% 6235.0 MT/day 45 C 6 bar
Component Urea Wt % 100.00% MT/day C bar H2O Flow rate Temperature Pressure
Chapter 05
Weight MT/day Wt % 31.8 0.37% 0.3 0.00% 8570.5 99.63% 8602.6 MT/day 52 C 6 bar
Chapter 06
CHAPTER 6
MATERIAL FLOW SHEET
Chapter 06
Chapter 07
CHAPTER 7
HEAT BALANCE CALCULATION
Chapter 07
+23 KJ/mol
NH2CONH2 + H2O
-60 KJ/mol
60 5.6
80 5.87
112 8.6
Ammonia Vapour T (C) Cp (KJ/KgK) 87 2.2 127 2.3 167 2.37 207 2.44
Chapter 07
Cp of the Carbamate
2.3 KJ/KgK
For NH3 liquid Cp = a + bT + cT2 5.6 = a + 333b + 3332c 5.87 = a + 353b + 3532c 8.6 = a + 385b + 385 c From (1), (2) & (3) a = 163.44 b = - 0.9338 c = 1.38*10-3
2
For NH3 gas Cp = a + bT + cT2 2.2 = a + 360b + 3602c 2.3 = a + 400b + 4002c 2.44 = a + 480b + 4802c From (4), (5) & (6) a = 0.4 b = 7.25*10-3 c = -6.25*10-6 (4) (5) (6)
For CO2 gas Cp = a + bT + cT2 0.84 = a + 300b + 3002c 0.94 = a + 400b + 4002c 1.01 = a + 500b + 500 c From (7), (8) & (9) Comprehensive design project 86
2
Chapter 07
For Urea Cp = a + bT + cT2 1.4 = a + 353b + 3532c 1.6 = a + 393b + 3932c 2.1 = a + 473b + 4732c From (10), (11) & (12) a = 1.08 b = -2.77*10-3 c = 1.04*10-5 (10) (11) (12)
Chapter 07
7.1.1 Reactor
190 C
170 C
170 C Q2 190 C
Q1 34 C
Low pressure steam load at 5 bar pressure and 151.8 C for ammonia heating
/day
Medium pressure steam load at 13 bar and 191.6 C for ammonia heating Comprehensive design project 88
Chapter 07
Medium pressure steam load at 15 bar and 198.3C for reactor heating
Chapter 07
7.1.2 Stripper
190 C
190C
MP STEAM COND.
198.3 C 198.3 C
178C
110 C
Chapter 07
7.1.3 Scrubber
189 C
150 C
190 C
153 C
Chapter 07
Energy loss
Chapter 07
STM 151.8 C
190 C
145 C
SC
170 C 170 C
Chapter 07
Production of steam load at 5bar Assume Cp of water at 145 C-150 C = 4.27 kJ/kg
Chapter 07
178 C
157 C
Chapter 07
Energy loss
157 C
COND. 151.8 C
129 C 80C
Chapter 07
Chapter 07
129 C
CW
Chapter 07
157 C
129 C
150 C
Chapter 07
Chapter 07
110 C
Heat loss
Chapter 07
MP steam load
110 C
Energy loss
Chapter 07
112 C
112 C
Chapter 07
Chapter 07
Chapter 08
CHAPTER 8
TABULATED HEAT BALANCE
Chapter 08
MJ/day
471962.08 300428.45 899260.67 123475.64 104259.64 97492.80 172190.9 416783.04 199581.49 63000.50 2848435.21
Output Energy
Heat out from Scrubber Heat out from Carbamate condenser Heat out from HPD Heat out from LP Absorber Heat out from HP Absorber Heat out from Wastewater cooling 1 Heat out from Wastewater cooling 2 Heat out from Granulator Heat out from Product Cooler Total output energy Table 8.1 Tabulated Heat Balance Comprehensive design project
MJ/day
124.70 1255586.69 6596.25 570330.38 251197.87 255948.00 512283.2 47434.75 62527.63 2962029.47
107
Chapter 08
113594.26 MJ/day
Total heat output greater than the total heat input. So this difference is due to heat generated in the reaction. But the amount of theoretical heat generated in the reaction is much higher than this value. That difference between actual and theoretical value happens because of the heat losses occurred during the process.
REFERENCES
Book References Urea manufacturing processes in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A27 Perry's Chemical Engineers' Handbook - Perry, R.H. and Green, D.W. (Editors) MARTYN S. RAY; DAVID W. JOHNSTON - Chemical Engineering Design Project: A Case Study Approach World Wide Web references Ammonia and Urea Production http://www.nzic.org.nz/ChemProcesses/production/1A.pdf Urea - http://www.stamicarbon.com/urea/_en/index.htm Urea - www.epa.gov/ttn/chief/ap42/ch08/final/c08s02.pdf Urea Production and Manufacturing process www.icis.com/v2/chemicals/9076560/urea/process.html Urea Wikipedia, the free encyclopedia - en.wikipedia.org/wiki/Urea Fertilizer Urea - www.extension.umn.edu/distribution/cropsystems/DC0636.html UREA - www.jtbaker.com/msds/englishhtml/u4725.htm Urea - www.3rd1000.com/urea/urea.htm MSDS safety data sheets for ammonium carbamate, urea, and ammonium from http://msds.chem.ox.ac.uk/ MSDS urea - http://www.sciencestuff.com/msds/C2950.html - Science Stuff Inc.,1104 Newport Ave, Austin, TX, USA MSDS urea - http://www.pusri.co.id/data/MSDS-urea.PDF E-book References The Environmental Impact of a Stamicarbon 2000 mtpd Urea Plant - Authors: Will Lemmen (Licensing Manager) and Hans van Baal (Licensing Manager) Latest Urea Technology for Improving Performance and Product Quality by EIJI SAKATA (Senior Process Engineer),TAKAHIRO YANAGAWA (PROCESS ENGINEER) --TOYO ENGINEERING CORPORATION , TOKYO JAPAN Escalating worldwide use of urea a global change contributing to coastal eutrophication by PATRICIA M. GLIBERT, JOHN HARRISON, CYNTHIA HEIL and SYBIL SEITZINGER
l e Steam g h f f TCW i j CW m
Water
TCW Cond. c
NH3
Steam
a) CO2 compressor b) Hydrogen removal reactor c) Urea reactor d) High-pressure stripper e) High-pressure carbamate condenser f) High-pressure scrubber g) Low-pressure absorber h) Low-pressure decomposer and rectifier i) Pre-evaporator j) Low-pressure carbamate condenser k) Evaporator l) Vacuum condensation section m) Process condensate treatment CW - Cooling water TCW - Tempered cooling water
k Steam
Cond.
CO2
NH3
i e c d f Water
g CO2 a b
Air
Urea
a) CO2 compressor; b) High pressure ammonia pump; c) Urea reactor; d) Medium-pressure decomposer; e) Ammonia carbamate separation column; f) Low-pressure decomposer; g) Evaporator; h) Prilling; i) Desorber (waste water stripper); j) Vacuum condensation section
pond
Garden
Guard room
Water tank
Cooling tower
Guard room
FLASH SEPARATOR
SCRUBBER SC
STM
BAG FILTER
CARBAMATE CONDENSER
UPPER SEPARATOR
STM HPD
SC
REACTOR HP ABSORBER STRIPPER LP ABSORBER GRANULATION SECTION CW PC STRIPPER SURFACE CONDENCER UREA GRANULES AIR HYDROLYSER
CW
CW CW UPC
AIR
LP steam
COMPRESSOR
NH3
CO2
Urea flow lines other process lines Steam line Condensed water line Cooling water line
BAG FILTER T FLASH SEPARATOR
T LOWER SEPARATOR
UPPER SEPARATOR
T P T STM
SC
GRANULATION SECTION
CO2
HP ABSORBER T CW
AIR
T LP steam
NH3
CO2
COOLING TOWER
POND WATER
Component Urea Wt % 12.79% 87.21% Component Urea H2O Wt % 79.49% NH3 Flow rate Temperature Pressure Weight MT/day Wt % 1060.6 338 0.5 75.81% 24.16% 0.04%
FLASH SEPARATOR
MT/day Wt % 1802 99.20% 14.5 0.80% Component Urea H2O Flow rate Temperature Pressure
H2O Flow rate Component Urea H2O NH3 Flow rate Temperature Pressure Weight MT/day Wt % 1060.3 232.4 0.3 82.00% 17.98% 0.02% Temperature Pressure
11.2 MT/day 189 C 175 bar Component NH3 CO2 Flow rate Temperature Pressure
1293 MT/day 110 C 0.7 bar Component Urea H2O Flow rate Weight Wt % 1060 99.20% 8.5 0.80% 112 C 2 bar
GRANULATOR
SCRUBBE R
Weight 263.3
Wt % 100.00%
ComponenWeight Wt % NH3 53.1 28.89% Carbamate 130.7 71.11% Flow rate Temperatu Pressure 183.8 MT/day 150 C 175 bar
Wt % 99.20%
PRODUC T COOLER
1068.5 MT/day
HPD
LOWER SEPARATOR
Temperature Pressure
Component Weight ComponenMT/day Wt % NH3 212.3 28.89% Carbamate 522.7 71.11% Flow rate Temperatu Pressure
CARBAMATE CONDENSER
Component Weight NH3 CO2 Flow rate Temperature Pressure 4.8 32.4
Wt % 12.79% 87.21%
Pressure Component Urea H2O NH3 Flow rate Temperature Pressure MT/day Wt % 1060.1 93.00% 79.7 0.1 6.99% 0.01%
SCREEN
Weight
Wt %
Component Urea H2O Air Flow rate Temperature Pressure Weight Component MT/day Wt % 1081.2 99.20% Urea H2O 8.7 0.80% Flow rate Temperature Pressure 1089.9 MT/day 89 C C 1 bar
Weight MT/day Wt % 10.6 0.45% 0.1 0.00% 2356.9 99.55% 2367.6 MT/day 55 C 6 bar
Weight MT/day Wt % 21.2 0.34% 0.2 0.00% 6213.6 99.66% 6235 MT/day 45 C 6 bar
MT/day Wt % 486.1 23.76% 1559.7 76.24% 2045.9 MT/day 170 C 175 bar
ComponenWeight Wt % NH3 612.4 44.89% CO2 751.8 55.11% Flow rate Temperatu Pressure 1364.3 MT/day 190 C 175 bar
Weight 9.5
Wt % 1.91%
MT/day Wt % 1060.6 75.81% 338 24.16% 0.5 0.04% 1399.1 MT/day 129 C 2.5 bar
UPPER SEPARATO R
Weight MT/day Wt % 20 94.79% 0.6 2.84% 0.5 2.37% 21.1 MT/day 129 C 2.6 bar
Component Weight Wt % NH3 600.7 100.00% Flow rate Temperature Pressure 600.7 MT/day 170 C 175 bar
Weight MT/day Wt % 1060 36.90% 591 20.57% 903.6 31.46% 318 11.07%
STRIPPER
HP ABSORB ER
LP ABSORBER
Component Component CO2 Flow rate Temperature Pressure Weight MT/day Wt % 263.3 100.00% 263.3 MT/day 170 C 175 bar Component CO2 Flow rate Temperature Pressure ht MT/d Wt % 77.3 100.00% 77.3 MT 80 C 20 bar Component H2O Urea NH3 Flow rate Temperature Pressure Weight MT/day Wt % 105.6 99.53% H2O Urea NH3 Flow rate Temperature Pressure
WWTPUNIT
CO2 COMPRESSOR